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US2601520A - Dialkenyl alkanephosphonates and polymers thereof - Google Patents

Dialkenyl alkanephosphonates and polymers thereof Download PDF

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US2601520A
US2601520A US101254A US10125449A US2601520A US 2601520 A US2601520 A US 2601520A US 101254 A US101254 A US 101254A US 10125449 A US10125449 A US 10125449A US 2601520 A US2601520 A US 2601520A
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diallyl
dialkenyl
polymers
compounds
radicals
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US101254A
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Harman Denham
Alan R Stiles
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Shell Development Co
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Shell Development Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40Esters thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus

Definitions

  • This invention relates to a new class of unsaturated phosphonates. .Moreparticularly. the invention provides unsaturated di'esters of alkan'ephosphonic acids and cyclic hydrocarbonsubstituted alkanephosphonic acids :and the polymers 'ofgsuch diesters.
  • the new esters are prepared byreacting unsaturated triesters of phosphorus. acid with the corresponding hydrocarbon halide.
  • the reac tion can be expressed byithe equation,
  • the new esters have been found "to exhibit properties which are predominantlylthose of unsaturated diesters of saturated aliphatic dibasic acids. They have been found to exhibit a pronounced resistance to burning and to impart a resistance to burning to compositions containingthem asa component of a mixture, in solution, or in the form of achemicallybound component.
  • the monomeric compounds of the invention which are colorless, oily liquids have proven to .be unique and particularly valuable plasticizers and modifying agents for many types of polymers.
  • the new esters polymerize to form particularly valuable polymers and copolymers having unique characteristics of color, clarity, hardness and resistnce to deterioration.
  • the newiesters are compounds o'f'the formula whereeach R representsan unsaturated'hydrocarbon radical and R represents an alkane radical which may be substituted by one or more cycloalkan'e' or aryl radicals.
  • Esters in which the radicals represented by R. are the allyl radicals or its terminally unsaturated homologs (radicals of the formula C(R)2C(R):CH2 where each R represents a hydrogen atom or an alkyl radical) are especially suitable.
  • dialkenyl alkanephosphonates and dialkenyl aralkanephosphonates in which each alkenyl radical contains the group -C--C:CH2 attached to the oxygen atom constitute particularly valuable subclasses of the new esters.
  • Illustrative examples of the compounds provided by the present invention include diallyl butanephosphonate, diallyl phenylmethanephosphonate, dicinriar'nyl methanephosphonate, dimethallyl eicosanephosphonate, divinyl para tolyl-methanephesphonate, divinyl 2-cyclohex ylethaneph'osphonate, po'ly(dia1ly'l *butanephosphonatei, -D0ly(diallyl phenylmethanephospho nate), dimethallyl propanephosphonate-dially1 phthalate copdlymer, diallyl 2 phenylpropanephosphonate diallyl mal'eate copolymer and divinyl pentanephosphonate -vinyl chloride co polymer.
  • the reaction is preferably conducted at about the reflux temperature of the reaction mixture under atmospheric pressure.
  • Illustrative examples of unsaturated triesters of phosphorus from which thecompounds ofthe presentv invention canbe prepared include triallyl .phosphite, trimethallyl phosphite, trivinyl phosphite, tri-Z-butenyl phosphite, -tri-isopropenylphosphite, tricinn-amyl phosphite and tri- 2-rcyclohex'ylallyl phosphite.
  • Illustrative examples .of hydrocarbon halides from which .the compounds of the present .inventioncan be prepared include .butyl chloride, benzyl chloride, .propyl .bromide, para-methylb nzyl iodide, cyclohexylmethyl chloride and tertiary-butyl chloride.
  • the polymeric compounds of the present invention are prepared by polymerizing or copolymerizing the monomeric compounds of the invention.
  • the polymerization is preferably conducted by heating the compounds in the presence'of; free radicals.
  • a wide varietyof procedures for polymerizing "organic compounds in the presence-30f 'free; radicals are known andcan suitably'be'employed to form the" polymericcompounds of the present-invention.
  • a particularly suitable procedure "consists of heating the monomers to "bepolymerized in the presenceof a peroxidic compound which 'decomposes to form free radicalsat a temperature at which the monomersand polymers are stable. The mixture is heated at about" the decomposition temperature of the peroxidic compound.
  • Illustrative examples of compounds which when heated with the monomeric compounds of the invention or mixtures of polymerizable compounds containing them initiate the formation of the polymers and copolymers provided by the present invention include (ii-tertiarybutyl peroxide, dibenzoyl peroxide, tertiarybutyl hydroperoxide, 2,2-bis(tertiary-butylperoxy) butane, tertiary-butyl perbenzoate and ditertiary-butyl diperoxalate.
  • Example I Diallyl phenylmethanephosphonate is produced by refluxing for hours at 130 C. a solution consisting of 126 grams of benzyl chloride and 100 grams of triallyl phosphite. The ester is isolated by a fractional distillation of the reaction mixture.
  • the diallyl phenylmethanephosphonate is a colorless, oily liquid having a boiling point of 144-145 C. under 0.5 mm. Hg pressure and a refractive index (n 20/D) of 1.5132.
  • the structure of the diallyl phenylmethanephosphonate is verified by the fact that the ester is found to contain 12.3% phosphorus and to have a molecular weight of 264.
  • Diallyl butanephosphonate is produced by refluxing for 20 hours at 70 C. a solution consisting of 500 grams of butyl chloride and 100 grams of triallyl phosphite.
  • the ester a colorless, oily liquid having a boiling point of 97-99 C. under 2 mm. Hg pressure and a refractive index (nZO/D) of 1.4553, is isolated by a fractional distillation of the reaction products.
  • diallyl butanephosphonate is found to contain 15.0% of phosphorus and to have a molecular weight of 212,- in good agreement with the value of 14.2% phosphorus and the molecular weight of 218 calculated from the formula for the product, namely I I Example III
  • Poly(dially1 phenylmethanephosphonate) is prepared by heating a solution consisting of 50 grams of diallyl phenylmethanephosphonatev and 0.5 gram of di-tertiary-butyl peroxide at a tem-- perature of 115 C. for 20 hours.
  • the colorless, water clear polymer is isolated by extracting or fractionally distilling off the unreacted monomers.
  • Example IV Poly(diallyl 'butanephosphonate) is prepared by heating .a solution consisting of 50 grams of diallyl butanephosphonate and 0.5 gram of ditertiary-butyl peroxide at a temperature of 115 C. for 20 hours. The colorless polymer is isolated by extracting or fractionally distilling off the unreacted monomers.
  • Example V A solid copolymer of diallyl butanephosphonate and diallyl phthalate is prepared by heating a solution consisting of grams of dially phthalate, 10 grams of diallyl butanephosphonate and 2 grams of benzoyl peroxide for 24 hours at 450 C., 6 hours at 90 C. and 18 hours at C. The polymer is isolated by extracting or fractionally distilling off the unreacted monomers and catalyst.
  • a polymer of a dialkenyl alkanephosphonate A dialkenyl carbocyclic-substituted alkanephosphonate.
  • a poly of a dialkenyl carbocyclic-substituted alkanephosphonate 8.

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Description

Patented June 24, 1952 DIALKENYL ALKANEPHOSPHONATES (AND POLYMERS THEREOF "Denham Harman and Alan R. Stiles,
Berkeley,
Calif., ass'ignors to Shell Development Com,- ;pany, San Francisco, Calif., a corporation of Delaware N Drawing. Application .J une 24,1949,
'Serial No. 101,254
12 Claims. 1
This invention relates to a new class of unsaturated phosphonates. .Moreparticularly. the invention provides unsaturated di'esters of alkan'ephosphonic acids and cyclic hydrocarbonsubstituted alkanephosphonic acids :and the polymers 'ofgsuch diesters.
The new esters are prepared byreacting unsaturated triesters of phosphorus. acid with the corresponding hydrocarbon halide. The reac tion can be expressed byithe equation,
The new esters have been found "to exhibit properties which are predominantlylthose of unsaturated diesters of saturated aliphatic dibasic acids. They have been found to exhibit a pronounced resistance to burning and to impart a resistance to burning to compositions containingthem asa component of a mixture, in solution, or in the form of achemicallybound component. By virtue of the predominantly saturated aliphatic characteristics of their acyl radicals, the monomeric compounds of the invention, which are colorless, oily liquids have proven to .be unique and particularly valuable plasticizers and modifying agents for many types of polymers. The new esters polymerize to form particularly valuable polymers and copolymers having unique characteristics of color, clarity, hardness and resistnce to deterioration.
The newiesters are compounds o'f'the formula whereeach R representsan unsaturated'hydrocarbon radical and R represents an alkane radical which may be substituted by one or more cycloalkan'e' or aryl radicals. 'Such esters .in which the radicals represented by R/are alkenyl havebeen found to provide monomers for .the formation of a preferred class of. polymers, partlcularly when the olefinic group is in a terminal position. Esters in which the radicals represented by R. are the allyl radicals or its terminally unsaturated homologs (radicals of the formula C(R)2C(R):CH2 where each R represents a hydrogen atom or an alkyl radical) are especially suitable. Thus, dialkenyl alkanephosphonates and dialkenyl aralkanephosphonates in which each alkenyl radical contains the group -C--C:CH2 attached to the oxygen atom constitute particularly valuable subclasses of the new esters.
Illustrative examples of the compounds provided by the present invention include diallyl butanephosphonate, diallyl phenylmethanephosphonate, dicinriar'nyl methanephosphonate, dimethallyl eicosanephosphonate, divinyl para tolyl-methanephesphonate, divinyl 2-cyclohex ylethaneph'osphonate, po'ly(dia1ly'l *butanephosphonatei, -D0ly(diallyl phenylmethanephospho nate), dimethallyl propanephosphonate-dially1 phthalate copdlymer, diallyl 2 phenylpropanephosphonate diallyl mal'eate copolymer and divinyl pentanephosphonate -vinyl chloride co polymer.
In preparing the monomeric compounds of the present invention byreacting the corresponding unsaturated triester of phosphorusacid with the corresponding hydrocarbon halide, the reaction is preferably conducted at about the reflux temperature of the reaction mixture under atmospheric pressure.
Illustrative examples of unsaturated triesters of phosphorus from which thecompounds ofthe presentv invention canbe prepared include triallyl .phosphite, trimethallyl phosphite, trivinyl phosphite, tri-Z-butenyl phosphite, -tri-isopropenylphosphite, tricinn-amyl phosphite and tri- 2-rcyclohex'ylallyl phosphite. V
Illustrative examples .of hydrocarbon halides from which .the compounds of the present .inventioncan be prepared include .butyl chloride, benzyl chloride, .propyl .bromide, para-methylb nzyl iodide, cyclohexylmethyl chloride and tertiary-butyl chloride.
The polymeric compounds of the present invention are prepared by polymerizing or copolymerizing the monomeric compounds of the invention. The polymerization is preferably conducted by heating the compounds in the presence'of; free radicals. A wide varietyof procedures for polymerizing "organic compounds in the presence-30f 'free; radicals are known andcan suitably'be'employed to form the" polymericcompounds of the present-invention. A particularly suitable procedure "consists of heating the monomers to "bepolymerized in the presenceof a peroxidic compound which 'decomposes to form free radicalsat a temperature at which the monomersand polymers are stable. The mixture is heated at about" the decomposition temperature of the peroxidic compound.
Illustrative examples of compounds which when heated with the monomeric compounds of the invention or mixtures of polymerizable compounds containing them initiate the formation of the polymers and copolymers provided by the present invention include (ii-tertiarybutyl peroxide, dibenzoyl peroxide, tertiarybutyl hydroperoxide, 2,2-bis(tertiary-butylperoxy) butane, tertiary-butyl perbenzoate and ditertiary-butyl diperoxalate.
The following examples are presented to illustrate in detail procedures by which the compounds provided by the present invention can suitably be prepared. As the compounds provided by the invention can have a variety of different structures, and in some cases can be prepared by other procedures, the invention is not to be construed as limited to the particular materials or conditions specified in the examples.
Example I Diallyl phenylmethanephosphonate is produced by refluxing for hours at 130 C. a solution consisting of 126 grams of benzyl chloride and 100 grams of triallyl phosphite. The ester is isolated by a fractional distillation of the reaction mixture. The diallyl phenylmethanephosphonate is a colorless, oily liquid having a boiling point of 144-145 C. under 0.5 mm. Hg pressure and a refractive index (n 20/D) of 1.5132. The structure of the diallyl phenylmethanephosphonate is verified by the fact that the ester is found to contain 12.3% phosphorus and to have a molecular weight of 264. These figures are in good agreement with the value of 12.2% phosphorus and the molecular weight of 253 calculated from the formula for the product, namely Example II Diallyl butanephosphonate is produced by refluxing for 20 hours at 70 C. a solution consisting of 500 grams of butyl chloride and 100 grams of triallyl phosphite. The ester, a colorless, oily liquid having a boiling point of 97-99 C. under 2 mm. Hg pressure and a refractive index (nZO/D) of 1.4553, is isolated by a fractional distillation of the reaction products. The diallyl butanephosphonate is found to contain 15.0% of phosphorus and to have a molecular weight of 212,- in good agreement with the value of 14.2% phosphorus and the molecular weight of 218 calculated from the formula for the product, namely I I Example III Poly(dially1 phenylmethanephosphonate) is prepared by heating a solution consisting of 50 grams of diallyl phenylmethanephosphonatev and 0.5 gram of di-tertiary-butyl peroxide at a tem-- perature of 115 C. for 20 hours. The colorless, water clear polymer is isolated by extracting or fractionally distilling off the unreacted monomers.
Example IV Poly(diallyl 'butanephosphonate) is prepared by heating .a solution consisting of 50 grams of diallyl butanephosphonate and 0.5 gram of ditertiary-butyl peroxide at a temperature of 115 C. for 20 hours. The colorless polymer is isolated by extracting or fractionally distilling off the unreacted monomers.
Example V A solid copolymer of diallyl butanephosphonate and diallyl phthalate is prepared by heating a solution consisting of grams of dially phthalate, 10 grams of diallyl butanephosphonate and 2 grams of benzoyl peroxide for 24 hours at 450 C., 6 hours at 90 C. and 18 hours at C. The polymer is isolated by extracting or fractionally distilling off the unreacted monomers and catalyst.
We claim as our invention:
. Diallyl butanephosphonate.
. Diallyl phenylmethanephosphonate.
. Poly(diallyl butanephosphonate).
A diallyl alkanephosphonate.
A dialkenyl alkanephosphonate.
A polymer of a dialkenyl alkanephosphonate. A dialkenyl carbocyclic-substituted alkanephosphonate.
8. A poly of a dialkenyl carbocyclic-substituted alkanephosphonate.
9. A dialkenyl alkanephosphonate in which both alkenyl radicals contain a lower 2-alkenyl group attached to the oxygen atom.
10. A dialkenyl arylalkanephosphonate in which both alkenyl radicals contain a lower 2-alkenyl group attached to the oxygen atom.
11. A phosphonic acid ester having the structure defined by the formula REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,397,422 Kosolopoff Mar. 26, 1946 2,425,766 Fon Toy Aug. 19, 1947 OTHER REFERENCES Kosolopoff: J. Am. Chem. Soc., 67, 2259-60. (Dec. 1945).
Chem. and Eng. News, 25, page 2030, July 14,
Fon Toy: J. Am. Chem. Soc.,.70, 1948).
186-188, (Jan.

Claims (1)

11. A PHOSPHONIC ACID ESTER HAVING THE STRUCTURE DEFINED BY THE FORMULA R''-P(OR)2 IN WHICH EACH R REPRESENTS A MONO-OLEFINICALLY UNSATURATED HYDROCARBON RADICAL AND R'' REPRESENTS A MEMBER OF THE GROUP CONSISTING OF ALKANE RADICALS AND CARBOCYCLIC-SUBSTITUTED ALKANE RADICALS.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2714100A (en) * 1952-08-05 1955-07-26 Victor Chemical Works Diallyl monochloromethanephosphonate and polymers
US2735789A (en) * 1956-02-21 Methods of flameproofing therewith
US2811469A (en) * 1952-08-05 1957-10-29 Victor Chemical Works Fabric flameproofing process
US2867610A (en) * 1953-09-22 1959-01-06 Victor Chemical Works Polymers and copolymers of dialkenyl beta-(carboxyalkyl) alkanephosphonates
US5128333A (en) * 1989-12-19 1992-07-07 Regents Of The University Of California Alkyl substituted phosphates and phosphonates as disruptants of insect sex pheromone-mediated behavior

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397422A (en) * 1945-03-24 1946-03-26 Monsanto Chemicals Esters of paraffin phosphonic acids
US2425766A (en) * 1945-10-29 1947-08-19 Victor Chemical Works Unsaturated alkyl esters of alkenyl phosphonic acids

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397422A (en) * 1945-03-24 1946-03-26 Monsanto Chemicals Esters of paraffin phosphonic acids
US2425766A (en) * 1945-10-29 1947-08-19 Victor Chemical Works Unsaturated alkyl esters of alkenyl phosphonic acids

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2735789A (en) * 1956-02-21 Methods of flameproofing therewith
US2714100A (en) * 1952-08-05 1955-07-26 Victor Chemical Works Diallyl monochloromethanephosphonate and polymers
US2811469A (en) * 1952-08-05 1957-10-29 Victor Chemical Works Fabric flameproofing process
US2867610A (en) * 1953-09-22 1959-01-06 Victor Chemical Works Polymers and copolymers of dialkenyl beta-(carboxyalkyl) alkanephosphonates
US5128333A (en) * 1989-12-19 1992-07-07 Regents Of The University Of California Alkyl substituted phosphates and phosphonates as disruptants of insect sex pheromone-mediated behavior

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